| Abstract
| - The adsorption of D2O on Pt(111) and the coadsorption with CO have been revisited by quantitative andin situ high-resolution X-ray photoelectron spectroscopy (XPS). During D2O adsorption at 110 K, O 1sspectra clearly show the known formation of a bilayer and multilayers. As indicated by a binding energychange of the multilayer peak in the XP spectra recorded during heating, a structural change in the D2Omultilayer at the onset of multilayer desorption (∼145 K) is observed. Coadsorption of CO and D2O leadsto occupation of bridge and on-top sites by CO, with the order in site occupation reversed as compared tothe clean surface, as previously observed. In addition, a new CO species is clearly resolved in C 1s spectra,which may be identified with CO on hollow sites. Upon D2O desorption, this new species disappears andthe CO site occupation changes to the value observed on the clean Pt(111). Induced by CO coadsorption,partial replacement of D2O from the surface into higher layers is observed, indicated by a reduced desorptiontemperature of water and an O 1s binding energy shift toward the value of the multilayer signal. Ourresults suggest an intermixed first layer of CO and D2O molecules; D2O on top of this layer also influencesthe CO site distribution. On a surface precovered with 0.5 monolayer (ML) of CO, D2O molecules can onlyadsorb on top of the CO layer and no mixed layer is formed; hence, no site change is observed. The preadsorbedD2O bilayer lowers the initial CO sticking coefficient by a factor of ∼13 as compared to the clean surface;this reduction is larger than previously detected.
|
